US3607918A - Preparation of n,n-dimethylterephthalamic acid and terephthalamides from terephthalic acid and aliphatic amides or nitriles - Google Patents
Preparation of n,n-dimethylterephthalamic acid and terephthalamides from terephthalic acid and aliphatic amides or nitriles Download PDFInfo
- Publication number
- US3607918A US3607918A US790455A US3607918DA US3607918A US 3607918 A US3607918 A US 3607918A US 790455 A US790455 A US 790455A US 3607918D A US3607918D A US 3607918DA US 3607918 A US3607918 A US 3607918A
- Authority
- US
- United States
- Prior art keywords
- acid
- terephthalic acid
- terephthalamides
- preparation
- nitriles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title abstract description 38
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical class NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 title abstract description 11
- 150000002825 nitriles Chemical class 0.000 title description 7
- 239000002253 acid Substances 0.000 title description 6
- 238000002360 preparation method Methods 0.000 title description 5
- 150000008431 aliphatic amides Chemical class 0.000 title description 2
- 239000000376 reactant Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 11
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical group CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical group NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- ATHHXGZTWNVVOU-UHFFFAOYSA-N monomethyl-formamide Natural products CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- OHLUUHNLEMFGTQ-AZXPZELESA-N n-methylacetamide Chemical group C[15NH]C(C)=O OHLUUHNLEMFGTQ-AZXPZELESA-N 0.000 claims description 2
- ATHHXGZTWNVVOU-VQEHIDDOSA-N n-methylformamide Chemical group CN[13CH]=O ATHHXGZTWNVVOU-VQEHIDDOSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 abstract description 8
- -1 alkyl cyanides Chemical class 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- LHIJETBHEKJGOK-UHFFFAOYSA-N 4-(dimethylcarbamoyl)benzoic acid Chemical compound CN(C)C(=O)C1=CC=C(C(O)=O)C=C1 LHIJETBHEKJGOK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- KXQRQBFRBYGAHV-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-dicarboxamide Chemical compound CN(C)C(=O)C1=CC=C(C(N)=O)C=C1 KXQRQBFRBYGAHV-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- SZYMPBOGVCHDEH-UHFFFAOYSA-N acetamide;n-methylacetamide Chemical compound CC(N)=O.CNC(C)=O SZYMPBOGVCHDEH-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- SCNOFCUSDSAHOM-UHFFFAOYSA-N formamide;n-methylformamide Chemical compound NC=O.CNC=O SCNOFCUSDSAHOM-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- MBHINSULENHCMF-UHFFFAOYSA-N n,n-dimethylpropanamide Chemical compound CCC(=O)N(C)C MBHINSULENHCMF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WRYRGDOADGEVPQ-UHFFFAOYSA-N propanenitrile Chemical compound C(CC)#N.C(CC)#N WRYRGDOADGEVPQ-UHFFFAOYSA-N 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
Definitions
- Terephthalamide N-methyl derivatives are prepared by reacting terephthalic acid with lower alkyl cyanides or with lower alkanoic amides or N-methyl derivatives, in oleum solution, at atmospheric pressure, and at 25C.l00 C.
- Terephthalamides have been prepared by reacting terephthaloyl chloride and an amine, or by reacting terephthalic acid and an amine. Both methods have disadvantages.
- the former requires the preparation of the acid chloride intermediate.
- the latter requires high pressure and temperatures, and the use of pressure equipment. It is a desideratum to prepare terephthalamides from readily available materials and without resort to pressure.
- This invention provides a process for preparing terephthalamides and N-methyl derivatives thereof that comprises reacting terephthalic acid with lower alkyl (C -C cyanides or with lower alkyl (c -C alkanoic acid amides or N-methyl derivatives, in oleum solution, at 25-l00 C.
- terephthalic acid This acid, usually prepared by catalytic oxidation of pxylene, is readily available commercially.
- the other reactants in the present process are lower (C -C cyanides and lower (C,-C alkanoic acid amides and their N-methyl derivatives. These compounds are readily prepared and most are commercially available. These reactants are methyl cyanide (acetonitrile); ethyl cyanide-(propionitrile); propyl cyanide (butyronitrile); formamide N-methylformamide; N,N-dimethylformamide; acetamide; N-methylacetamide; N,N-dimethylacetamide; propionamide; N-methylporpionamide; and N,N-dimethylpropionamide.
- the process of this invention is carried out at atmospheric pressure and at temperatures between about 25 C. and about 100 C. Temperatures between about 75 C. and about 85 C.
- Reaction time can vary between about 1 hour and about hours.
- the solvent used in oleum having an S0,, content between about percent and about 8 percent, on a weight basis, i.e., 15 percent to 80 percent oleum.
- the concentration of terephthalic acid in oleum can be between about 0.5 mole and about 7 moles per liter of oleum, depending upon the 80;, content; the higher content of SO dissolving more moles of terephthalic acid.
- the molar ratio of nitrile or amide to terephthalic acid is at least stoichiometric (2:1) up to about 4:1. Higher ratios can be used, but serve no useful purpose and unduly increase the amount of material to be handled.
- N-Methylformamide (21.9 g., 0.3 mole) and terephthalic acid (16.6 g., 0,1 mole) were charged to a 250 ml. round-bot? tom flask, along with 100 ml. of 30 S0 in H 50 The solution was heated at 80 C. for 360 minutes. The reaction mix- .ture was cooled and poured onto ice. The precipitate was collected, washed, and dried. The yield of N, N-dimethylterephthalamide was 83%.
- EXAMPLE 6 N,N-Dimethylacetamide (26.4 g., 0.3 mole) and terephthalic acid (16.6 g., 0.1 mole) were charged to a 250 ml. roundbottom flask, along with 100 m1, of 30% SO, in H SQ The flask was heated to 110 C. for 400 minutes. The reaction was cooled and poured onto ice. Filtration, followed by extraction of the mother liquor with ether, and evaporation gave 36% yield of N,N-dimethylterephthalamic acid.
- a process for preparing terephthalamide and N-methyl' derivatives thereof and N,N-dimethylterephthalamic acid that comprises reacting terephthalic acid with a reactant selected from the group consisting of lower alkyl (c -C acid amides, in 15 percent to 80 percent oleum solution, at 25-100 C., using between about 0.5 mole and about 7 moles terephthalic acid per liter of oleum and at least the stoichiometric amount of said reactant to terephthalic acid.
- a reactant selected from the group consisting of lower alkyl (c -C acid amides, in 15 percent to 80 percent oleum solution, at 25-100 C.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Terephthalamide N-methyl derivatives are prepared by reacting terephthalic acid with lower alkyl cyanides or with lower alkanoic amides or N-methyl derivatives, in oleum solution, at atmospheric pressure, and at 25* C.- 100* C.
Description
United States Patent Anthony T. Jurewicz Middlesex, NJ. 790,455
Jan. 10, 1969 Sept. 21,1971
Mobil Oil Corporation [72] Inventor [21 Appl. No. [22] Filed [45] Patented [73] Assignee [54] PREPARATION OF N,N-
DIMETI-lYLTEREPI-lTI-IALAMIC ACID AND TEREPIITI-IALAMIDES FROM TEREPI-ITIIALIC ACID AND ALIPHATIC AMIDES OR NITRILES 6 Claims, No Drawings 52 us. Cl 260/518 R,
260/558 A 5 l] Int. Cl C070 103/33 Primary Examiner-Henry R. Jiles Assistant ExaminerHarry l. Moatz Attorneys-Oswald G. Hayes, Andrew L. Gaboriault and Hastings S. Trigg ABSTRACT: Terephthalamide N-methyl derivatives are prepared by reacting terephthalic acid with lower alkyl cyanides or with lower alkanoic amides or N-methyl derivatives, in oleum solution, at atmospheric pressure, and at 25C.l00 C.
PREPARATION OF N,N-DIMETIIYLTEREPI-ITI-IALAMIC ACID AND TEREPI'ITI-IALAMIDES FROM TEREPHTI-IALIC ACID AND ALIPI-IATIC AMIDES OR NITRILES BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to the preparation of amides. It is more particularly concerned with the preparing of terephthalamides and N-methyl derivatives from terephthalic acid and fatty acid amides or nitriles.
2. Description of the Prior Art Terephthalamides have been prepared by reacting terephthaloyl chloride and an amine, or by reacting terephthalic acid and an amine. Both methods have disadvantages. The former requires the preparation of the acid chloride intermediate. The latter requires high pressure and temperatures, and the use of pressure equipment. It is a desideratum to prepare terephthalamides from readily available materials and without resort to pressure.
SUMMARY OF THE INVENTION This invention provides a process for preparing terephthalamides and N-methyl derivatives thereof that comprises reacting terephthalic acid with lower alkyl (C -C cyanides or with lower alkyl (c -C alkanoic acid amides or N-methyl derivatives, in oleum solution, at 25-l00 C.
DESCRIPTION OF SPECIFIC EMBODIMENTS One reactant in the process of this invention is terephthalic acid. This acid, usually prepared by catalytic oxidation of pxylene, is readily available commercially. I
The other reactants in the present process are lower (C -C cyanides and lower (C,-C alkanoic acid amides and their N-methyl derivatives. These compounds are readily prepared and most are commercially available. These reactants are methyl cyanide (acetonitrile); ethyl cyanide-(propionitrile); propyl cyanide (butyronitrile); formamide N-methylformamide; N,N-dimethylformamide; acetamide; N-methylacetamide; N,N-dimethylacetamide; propionamide; N-methylporpionamide; and N,N-dimethylpropionamide.
The process of this invention is carried out at atmospheric pressure and at temperatures between about 25 C. and about 100 C. Temperatures between about 75 C. and about 85 C.
are preferred. Reaction time can vary between about 1 hour and about hours. The solvent used in oleum having an S0,, content between about percent and about 8 percent, on a weight basis, i.e., 15 percent to 80 percent oleum. In general, the concentration of terephthalic acid in oleum can be between about 0.5 mole and about 7 moles per liter of oleum, depending upon the 80;, content; the higher content of SO dissolving more moles of terephthalic acid. The molar ratio of nitrile or amide to terephthalic acid is at least stoichiometric (2:1) up to about 4:1. Higher ratios can be used, but serve no useful purpose and unduly increase the amount of material to be handled.
EXAMPLE 1 Terephthalic acid (16.6 g., 0.1 mole) and N-methylacetamide (21.9 g., 0.3 mole) were charged to a 250 ml. round-bottom flask, along with 100 ml. of 30% S0 in H 80 The solution was heated at 80 C. for 300 minutes. The reaction mixture was cooled and poured onto 500 g. of ice. A precipitate was obtained. This was collected, washed with water, and dried. The yield of solid was 83% (16 g.). Analysis by infrared, NMR, and melting point (315-3l7) showed the structure to he N, N-dimethyl terephthalamlde.
EXAMPLE 2 Terephthalic acid (16.6 g. 0.1 mole) and acetamide (17.7 g., 0.3 mole) were charged to a 250 ml. round-bottom flask, along with 100 ml. of 30% 30;, in H 50 The solution was heated at C. for 360 minutes. The reaction mixture was cooled and poured onto 500g. of ice. A precipitate was obtained, which was collected, washed and dried. The yield was (16.0. g.). Analysis by infrared and NMR showed the structure to be terephthalamide.
EXAMPLE 3 Acetonitrile (12.3 g., 0.3 mole) was charged to a 250 ml. round-bottom flask containing terephthalic acid (16.6 g., 0.1 mole) in ml. of 30% SO, in H 80 at 20 C. After the addition was completed, the mixture was heated at 80 C. for 360 minutes. The reaction mixture was cooled and poured onto ice. A precipitate was obtained, which was collected, washed,
and dried. The yield was 90% (14.9 g.). Analysis by infrared and NMR showed the structure to be terephthalamide.
EXAMPLE 4 Terephthalic acid (16.6 g., 0.1 mole) and formamide (13.8 g., 0.3 mole) were charged to a 250 ml. round-bottom flask, along with 100 ml. of 30% 80;, in H 50 The mixture was heated at C. for 360 minutes. The reaction mixture was cooled and poured onto ice. The precipitate was collected, washed, and dried. A 69% yield to terephthalamide was obtained.
EXAMPLE 5 N-Methylformamide (21.9 g., 0.3 mole) and terephthalic acid (16.6 g., 0,1 mole) were charged to a 250 ml. round-bot? tom flask, along with 100 ml. of 30 S0 in H 50 The solution was heated at 80 C. for 360 minutes. The reaction mix- .ture was cooled and poured onto ice. The precipitate was collected, washed, and dried. The yield of N, N-dimethylterephthalamide was 83%.
EXAMPLE 6 EXAMPLE 7 N,N-Dimethylacetamide (26.4 g., 0.3 mole) and terephthalic acid (16.6 g., 0.1 mole) were charged to a 250 ml. roundbottom flask, along with 100 m1, of 30% SO, in H SQ The flask was heated to 110 C. for 400 minutes. The reaction was cooled and poured onto ice. Filtration, followed by extraction of the mother liquor with ether, and evaporation gave 36% yield of N,N-dimethylterephthalamic acid.
Although the present invention has been described with preferred embodiments, it is to be understood that modifications and variations may be resorted to, without departingv from the spirit and scope of this invention, as those skilled in the art will readily understand. Such variations and modifida-- tions are considered to be within the purview and scope of the appended claims.
I claim:
1. A process for preparing terephthalamide and N-methyl' derivatives thereof and N,N-dimethylterephthalamic acid that comprises reacting terephthalic acid with a reactant selected from the group consisting of lower alkyl (c -C acid amides, in 15 percent to 80 percent oleum solution, at 25-100 C., using between about 0.5 mole and about 7 moles terephthalic acid per liter of oleum and at least the stoichiometric amount of said reactant to terephthalic acid.
2. The process of claim I, wherein said reactant is N- methylacetamide.
3. The process of claim I, wherein said reactant is acetamide.
mide.
6. The process of claim 1, wherein said reactant is N- methylformamide.
23%;? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 7,9 Dated September 21, 1971 Inventor(s) Anthony T. Jurewicz It is certified that: error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 1, line 18, change "pressure" to --pressures-- Column 1, line 27, change "(c -C to "(c -c Column 1, line +0, after "formamide" should be Column 1, line +8, change "in" to --is-- Column 1, line 49, change "8" to --80-- Column 1, line 69, change "317-" to --317-- Column 2, line 67, change "(c -C to (C -C Signed and sealed this 25th da'y of April 1972.
(SEAL) Atheist:
EDWARD M.FLETCH 5F1,JR. ROBERT GOTISCHALK Attaching Officer Commissioner of Patents
Claims (5)
- 2. The process of claim 1, wherein said reactant is N-methylacetamide.
- 3. The process of claim 1, wherein said reactant is acetamide.
- 4. The process of claim 1, wherein said reactant is acetonitrile.
- 5. The process of claim 1, wherein said reactant is formamide.
- 6. The process of claim 1, wherein said reactant is N-methylformamide.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79045569A | 1969-01-10 | 1969-01-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3607918A true US3607918A (en) | 1971-09-21 |
Family
ID=25150730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US790455A Expired - Lifetime US3607918A (en) | 1969-01-10 | 1969-01-10 | Preparation of n,n-dimethylterephthalamic acid and terephthalamides from terephthalic acid and aliphatic amides or nitriles |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3607918A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4053510A (en) * | 1974-03-06 | 1977-10-11 | Akzo N.V. | Process for the production of aromatic and cycloaliphatic dicarboxylic acid diamides |
-
1969
- 1969-01-10 US US790455A patent/US3607918A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4053510A (en) * | 1974-03-06 | 1977-10-11 | Akzo N.V. | Process for the production of aromatic and cycloaliphatic dicarboxylic acid diamides |
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